Coumarin and coumarinimide derivatives

ABSTRACT

Compounds of the formula ##SPC1## 
     In which 
     X signifies oxygen or =NH, 
     R 1  signifies an alkyl, alkenyl or phenyl radical which is unsubstituted or substituted, 
     R 2  signifies hydrogen or one of the meanings of R 1  or 
     R 1  and R 2  together with the vicinal nitrogen atom form a heterocyclic ring system, 
     R 3  signifies hydrogen, acyl or an alkyl or phenyl radical which is unsubstituted or substituted, and 
     R 4  signifies the atoms needed to complete an aromatic carbocyclic or heterocyclic ring system, 
     And the ring A and chain R 4  are unsubstituted or substituted, 
     Are useful fluorescent dispersion dyestuffs.

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

The present invention relates to new coumarin and coumarinimidederivatives, which are fluorescent dispersion dyestuffs.

The invention provides a compound, free of carboxyl and sulphonic acidgroups, of formula I, ##SPC2##

in which

X signifies oxygen or =NH,

R₁ signifies an alkyl, alkenyl or phenyl radical which is unsubstitutedor substituted,

R₂ signifies hydrogen or one of the meanings of R₁, or

R₁ and R₂ together with the vicinal nitrogen atom form a heterocyclicring system,

R₃ signifies hydrogen, acyl or an alkyl or phenyl radical which isunsubstituted or substituted, and

R₄ signifies the atoms needed to complete an aromatic carbocyclic orheterocyclic ring system,

And the ring A and chain R₄ are unsubstituted or substituted.

Any alkyl or alkenyl groups in the molecule may be straight-chain orbranched, and contain 1 to 7 carbon atoms, the alkyl groupspreferentially 1, 2, 3 or 4 carbon atoms. The alkyl groups may also becyclic; cyclohexyl or methylcyclohexyl groups are preferred cycloalkylradicals.

Suitable substituents for the substituents on formula I include, forexample, one or more halogen atoms (in particular chlorine and bromineatoms), alkoxy, hydroxy, cyano, thiocyano, vinyl, amino, alkylamino,dialkylamino, phenylamino, N-phenyl-N-alkylaminio, phenyl, phenoxy,acyl, acyloxy or acylamino groups. Specially preferred on account ofprice are unsubstituted methyl or ethyl groups.

Any phenyl groups in the molecule and also the nuclei designated A andR₄ may carry the substituents named above, or an alkyl, trifluoromethylor nitro group.

If R₁ and R₂ together with the nitrogen atoms linked with themconstitute a heterocyclic ring system, this generally means a 5- or6-membered ring which, as described above, may carry substituents, andwhich may contain in addition to the =CH or --CH₂ groups, otherheteroatoms -- in particular oxygen, sulphur or nitrogen atoms -- andmay be saturated or unsaturated.

R₄ completes a benzene ring preferentially, though it may also completea pyridine, pyrimidine, pyrryl, pyrazolyl or imidazolyl ring. Thesegroups may have other rings attached, yielding, for example,naphthalene, quinoline or indole structures.

Preferred acyl groups are of the formula R--Y-- or R'--Z--, in which Rdenotes a hydrocarbon radical which may carry the substituents mentionedabove and/or contain heteroatoms, preferentially an alkyl or phenylradical which may be substituted,

Y is a radical --O--CO--, --SO₂ -- or --O--SO₂ --,

R' is a hydrogen atom or R,

Z is a radical --CO--, --NR"CO-- or --NR"SO₂ --

R" is a hydrogen atom or R.

Of particular interest are compounds of formula Ia, ##SPC3##

in which

X signifies oxygen or =NH,

R₅ signifies alkyl which is unsubstituted or substituted by hydroxyl,alkoxy, cyano, formyloxy, alkylcarbonyloxy, alkoxycarbonyloxy,alkoxycarbonyl or benzoyloxy as substituents, allyl or phenyl,

R₆ signifies hydrogen or one of the meanings of R₅,

R₇ signifies a radical of the formula:

    --CH = R.sub.8 -- CH = R.sub.9 *

in which R₈ and R₉ independently signify =CH-- or =N-- which isunsubstituted or substituted by chlorine, bromine, methyl, alkoxy,cyano, thiocyano, trifluoromethyl, alkoxycarbonyl, benzyloxycarbonyl,alkylcarbonyloxy, acetylamino, propionylamino, benzoylamino,aminosulphonyl, alkylaminosulphonyl, dialkylaminosulphonyl,phenylaminosulphonyl or N-alkyl-N-phenylaminosulphonyl, or a radical ofthe formula: ##SPC4##

in which

R₁₀ signifies aminosulphonyl, alkylaminosulphonyl ordialkylaminosulphonyl, and

the end denoted with * is linked to the carbon atom marked similarly informula Ia, and

the alkyl and alkoxy groups named contain 1 to 4 carbon atoms.

More preferred compounds are those of formula Ib, ##SPC5##

in which

R₁₁ signifies ethyl, which is unsubstituted or substituted by cyano,acetoxy, propionyloxy, methoxycarbonyl, ethoxycarbonyl,methoxycarbonyloxy or ethoxycarbonyloxy,

R₁₂ signifies allyl, phenyl or one of the meanings of R₁₁,

R₁₃ signifies a radical of the formula:

    --CH = R.sub.8 -- CH = CH--* ,

which is unsubstituted or substituted by chlorine, bromine, methyl,methoxy, ethoxy, cyano, thiocyano, trifluoromethyl, methoxycarbonyl,ethoxycarbonyl, aminosulphonyl, methylaminosulphonyl ordimethylaminosulphonyl, with the end denoted * linked to the carbon atommarked similarly in formula Ib,

and R₈ denotes = CH-- or = N--.

Specially preferred compounds are those of formula Ic, ##SPC6##

in which

R₁₁, r₁₂ and X are as defined above,

R₁₄ and R₁₆ each independently signify hydrogen, chlorine, bromine,methyl, methoxy, cyano or trifluoromethyl,

R₁₅ signifies methoxycarbonyl, ethoxycarbonyl or one of thesignificances given above for R₁₄ /R₁₆, and

R₁₇ signifies aminosulphonyl, methylaminosulphonyl,dimethylaminosulphonyl or one of the meanings given under R₁₄ /R₁₆.

The invention also provides a process for producing compounds of formulaI, comprising

a. condensing a compound of formula II, ##SPC7##

in which R₁, R₂ and A are as defined above,

with a compound of formula III, ##SPC8##

in which R₃ and R₄ are as defined above,

to form a compound of formula I', ##SPC9##

in which R₁ to R₄ and A are as defined above, or

b. hydrolysing a compound of formula I' and splitting off ammonia, toform a compound of formula I", ##SPC10##

in which R₁ to R₄ and A are as defined above.

The condensation of the aldehyde of formula II with the compound offormula III in process variant (a), is suitably effected in an inert,preferably anhydrous solvent, such as ethanol, methanol,dimethylformamide, dimethylsulphoxide or dioxane. The reaction ispreferably carried out in the presence of an organic base such aspiperidine, pyrrolidine or pyridine, and is suitably effected attemperatures from 30° to 180°C, preferably at the boiling point of thesolvent in question, under reflux. Where an alcohol is used as solvent,the coumarinimides occur as an insoluble product during the course ofthe reaction. The compounds of formula I' are usually obtained in a verypure state and with excellent yields, and may be isolated inconventional manner, for example, by concentration and filtering-off.

In process variant (b), hydrolysis of the compound of formula I' may beaccomplished in conventional manner, such as by boiling in organic acids(e.g. acetic acid) or diluted mineral acids (1 to 10% hydrochloricacid). Here it may be of advantage to add a water-soluble organicsolvent (such as methanol or ethanol) to the dilute mineral acid. It isbelieved that the ring substituted by the imine group is cracked byhydrolysis, then splitting off ammonia causes ring closure. Theseparation of ammonia and with it the ring closure to the coumarincompound of formula I" occur practically simultaneously, under thepreferred reaction conditions.

The compounds of formula III are new and may, for example, be obtainedby the condensation of a compound of formula IV, ##SPC11##

in which R₃ and R₄ are as defined above, with cyanoacetic acid,cyanoacetic alkyl ester (alkyl of 1 to 4 carbon atoms) or cyanoaceticchloride. The reactants are preferably used in approximately equivalentamounts. The reaction is preferably effected in a polar solvent of highboiling point (e.g. dimethylformamide), and preferably at temperaturesfrom 140° to 200°C, more preferably at about 160°C. It is preferred touse an acid-binding medium such as piperidine or sodium carbonate. Thereaction lasts 5 to 10 hours under preferred conditions. Isolation ofthe product may be achieved, for example, by pouring on water, in whichthe compound of formula III has only very poor solubility. The reactionsolution may also be cooled down to about 90° - 100°C and water addeduntil there is a slight turbidity, after which cooling is continued, andthe compound of formula III crystallizes out in very pure form.

Those compounds whose preparation is not specifically described may beprepared by methods known in the literature or methods analogous toknown methods or to methods described herein, from known startingmaterials.

The compounds of formula I may be processed into dyeing preparations ina generally familiar manner, e.g. by milling in the presence ofdispersing agents and/or fillers. With the dried preparations, which arepossibly dried by atomization or under vacuum, after adding more or lesswater it is possible to dye, pad or print, with a so-called long orshort liquor. The dyestuffs are usually absorbed excellently from theaqueous suspension formed onto textile materials of synthetic orsemisynthetic, hydrophobic organic substances of high molecular weight.They are particularly indicated for dyeing or printing textiles oflinear, aromatic polyesters, as well as those of cellulose-21/2-acetate,cellulose triacetate and polyamide synthetics. Dyeing or printing isdone by conventional techniques, such as that described in French Pat.No. 1,445,371.

The dyeings obtained generally have good fastnesses, particularly tolight, thermosetting, sublimation and pleating. They have also generallygood wet-fastness, e.g. against water, sea water, washing andperspiration, and fastness to solvents, in particular dry cleaningfluids, to textile lubricants, to rubbing, to cross-dyeing, to ozone, toflue gas and to chlorine. They are generally resistant to the action ofthe various permanent press processes and the so-called soil-releasefinishes. The reduction resistance (when dyeing wool) and the resistwith wool and cotton are also usually good.

The new compounds according to the invention may also, especially afterthe processing or conditioning usual with pigment dyestuffs, be suitablefor, say, dyeing bulk plastics, including plastics or synthetic resinscontaining solvents or free of these (in paints with oil or water base,in lacquers of various kinds, for spin-dyeing viscose,polyacrylonitrile, aromatic polyesters or cellulose acetate, forpigmenting polyethylene, polypropylene, polystyrene, polyvinyl chloride,rubber and artificial leather). They may also be suitable for inks usedby the printing industry, for pulp dyeing, for coating textiles or forpigment printing.

The dyeings obtained are usually light- and migration-fast. Theydistribute well in plastics, stand up well to solvents and paintingover, and have good transparency.

The very frequently observed phenomenon of mixtures of dyestuffsexcelling single dyestuff components in affinity can be observed in thiscase too. Hence the cheaper compounds of formula I, not substituted inthe nucleus R₄ or substituted in simple fashion, may be usedadvantageously as mixtures.

In the Examples that follow, the parts are parts by weight and thepercentages are weight percentages. The temperatures are given indegrees Centigrade.

EXAMPLE 1

a. 33.15 parts 3-cyanomethyl-1,2,4-benzothiadiazine-1,1-dioxide and28.95 parts 4-N-diethylamino-2-hydroxybenzaldehyde are dissolved in 300parts ethanol and after adding 5 parts piperidine heated quickly toboiling point. The deep yellow reaction product forms almost at oncewith almost 100% yield and is precipitated. After cooling it is filteredand dried. A recrystallized sample from dimethylformamide had a meltingpoint of 282°-283° (uncorr.).

Elementary analysis

            C       H         N         S                                         ______________________________________                                        Found:    60.4 %    5.1 %     13.7 %  8.1 %                                   Calculated:                                                                             60.6 %    5.1 %     14.1 %  8.1 %                                   ______________________________________                                    

The mass spectrum (m/e=396), the 100 MHz proton resonance spectrum andthe IR data are valid for the empirical formula C₂₀ H₂₀ N₄ O₃ S and thefollowing structure: ##SPC12##

The electron spectrum (in dimethyl sulphoxide) is:

    λ = 280.5 mμ   (log ε = 4.04)                               λ.sub.max = 462 mμ                                                                           (log ε = 4.70)                           

b. To produce the corresponding coumarin compound, 56.7 parts of thecompound produced above in (a), are suspended in a mixture of 300 partsethanol and 200 parts hydrochloric acid (5%) and boiled vigorously forfour hours under reflux. The ring cleavage and reclosure take place withvirtually 100% yield. After cooling the product is filtered, washed freeof acid and dried. Without further treatment it can be made up into adispersed dyestuff. As such it will dye polyester fibre materials tobrilliant yellow shades with strong greenish fluorescence, characterizedby excellent fastness properties.

A sample of dyestuff obtained in accordance with the above procedure b),recrystallized twice from dimethylformamide, had a boiling point of320°-321° (uncorr.).

Elementary analysis

            C       H         N         S                                         ______________________________________                                        Found:    60.5 %    4.9 %     10.7 %  8.2 %                                   Calculated:                                                                             60.4 %    4.8 %     10.6 %  8.1 %                                   ______________________________________                                    

The mass spectrum (m/e = 397), the 100 MHz proton resonance spectrum andthe IR data correspond to the empirical formula C₂₀ H₁₉ N₃ O₄ S and thefollowing structure: ##SPC13##

The electron spectrum (in dimethyl sulphoxide) is:

    λ.sub.1 = 280 mμ                                                                             (log ε = 4.01)                               λ.sub.max = 456 mμ                                                                           (log ε = 4.76)                           

Fluorescence spectrum in dimethylformamide:

    Excitation maximum:     456 mμ                                             Emission band:          498 mμ                                             In dioxane:                                                                   Excitation maximum:     440 mμ                                             Emission band:          472 mμ                                         

c. The starting material3-cyanomethyl-1,2,4-benzothiadiazine-1,1-dioxide is prepared as follows:

61 parts 1-aminobenzene-2-sulphonamide (produced according to theinstructions of Helv. 12, 667 ff, (1929) by sulphonation of1-chloro-2-nitrobenzene with sodium sulphide, oxychlorination of theresulting 2,2'-dinitrodiphenyl bisulphide-1,1' to1-nitrobenzene-2-sulphochloride, amidation with ammonia to thecorresponding sulphonamide and reduction of the nitro group to the aminogroup) and 47 parts of cyanoacetic ethyl ester are held for 5 hours at160° in 170 parts dimethyl acetamide. Ethanol and water separatingduring the reaction are remove by distillation. After this the reactionmixture is cooled to about 100° and hot water is added to it until aslight turbidity appears. With further cooling the reaction product isprecipitated. After filtration and drying a solid product is obtained,which after recrystallization from dimethylformamide has a melting pointof 200°.

The product was analyzed and gave the following values:

molecular weight 221 (measured by mass spectrography),

Elementary analysis:

             C     H       N          S                                           ______________________________________                                        (C.sub.9 H.sub.7 N.sub.3 O.sub.2 S)                                                      48.7    3.2     19.0   14.8 Found                                             48.8    3.17    19.0   14.5 Calculated                             ______________________________________                                    

NMR spectrum at 60 MHz (in deuterated dimethyl sulphoxide):

    Methylene:                                                                              4.25         PPM = 2 H (singlet)                                    Aromatic                                                                      hydrogens:                                                                              7.2 - 7.95   PPM = 4 H (multiplet)                              

from which the following structural formula can be deduced: ##SPC14##

(3-cyanomethyl-1,2,4-benzothiadiazine-1,1-dioxide).

For the dyestuffs in the table following, the substituents are given inaccordance with formula Ia. These dyestuffs are produced according tothe procedure in Example 1, and their structure and propertiesestablished according to the method described previously.

The linkage point on the chain designated R₇ is again marked with *where necessary. Dyed onto polyester fibre material, all dyestuffs giveyellow dyeings fluorescing with a strong greenish tint. Each examplerepresents two dyestuffs, one in which the X symbol denotes oxygen andone in which the X signifies an imino group; the two dyestuffs are verysimilar in their properties.

                                      TABLE                                       __________________________________________________________________________    Exple.                                                                        No. R.sub.5       R.sub.6      R.sub.7                                        __________________________________________________________________________    2   --CH.sub.2 CH.sub.2 CN                                                                      --CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            --CH=CH--CH=CH--                               3   --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                       --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      do.                                            4   --CH.sub.2 CH.sub.2 OH                                                                      --CH.sub.2 CH.sub.2 CN                                                                     do.                                            5   --CH.sub.2 CH.sub.2 OCHO                                                                    --CH.sub.2 CH.sub.2 OCHO                                                                   do.                                            6   --CH.sub.2 CH.sub.2 COOCH.sub.3                                                             --CH.sub.3   do.                                            7   --CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                      --CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                     do.                                            8   --CH.sub.2 CH.sub.2 OCOOCH.sub.3                                                            --CH.sub.2 CH.sub.2 OCOOCH.sub.3                                                           do.                                            9   --CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5                                                     --CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5                                                    do.                                            10  --CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9                                                      --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      do.                                            11  --CH.sub.2 CH(CH.sub.3)OCOCH.sub.3                                                          --CH.sub.2 CH(CH.sub.3)OCOCH.sub.3                                                         do.                                            12  -- CH.sub.2 CH.sub.2 CH.sub.3                                                               --CH.sub.2 CH.sub.2 CH.sub.3                                                               do.                                            13  --CH.sub.2 CH.sub.2 OCOOCH.sub.2 CH.sub.2 CH.sub.3                                          --CH.sub.3   do.                                            14  --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                       --CH.sub.2 CH.sub.2 COOCH(CH.sub.3).sub.2                                                  --CH=CH--CH=CH--                               15  --CH.sub.2 CH.sub.2 CN                                                                      --CH.sub.2 CH.sub.2 CN                                                                     do.                                            16  --C.sub.2 H.sub.5                                                                           --C.sub.2 H.sub.5                                                                          do.                                            17  --CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                        --CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       do.                                            18  --CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5                                                      --C.sub.2 H.sub.5                                                                          do.                                            19  --CH.sub.2 --CH=CH.sub.2                                                                    do.          do.                                            20  --CH.sub.2 CH.sub.2 CN                                                                      H            --CH=C(NHCOC.sub.2 H.sub.5)--CH=CH--           21  --CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             H            --CH=C(NHCOC.sub.6 H.sub.5)--CH=CH--           22  --C.sub.2 H.sub.5                                                                           --C.sub.2 H.sub.5                                                                          --CH=C(OCH.sub.3)--C(OCH.sub.3)=CH--           23  do.           do.          *--CH=C(SCN)--CH=CH--                          24  do.           do.          --CH=C(Cl)-- C(Cl)=CH--                        25  do.           do.          --CH=C(Br)--C(Br)=CH--                         26  do.           do.          *--CH=C(Cl)--CH=CH--                           27  do.           do.          *--CH--C(CF.sub.3)--CH=CH--                    28  --C.sub.2 H.sub.5                                                                           --C.sub.2 H.sub.5                                                                          *--CH=C(Cl)--CH=C(Cl)--                        29  do.           do.          *--CH=C(Cl)--C(CH.sub.3)=CH--                  30  do.           do.          *--C(CH.sub.3)=CH--CH=CH--                     31  do.           do.          *--C(Cl)=C(Cl)--C(Cl)=C(Cl)--                  32  do.           do.          *--CH=C(CN)--CH=CH--                           33  do.           do.          *--CH=CH--C(COOCH.sub.3)=CH--                  34  do.           do.          *--CH=CH--C(COOC.sub.2 H.sub.5)=CH--           35  do.           do.          *--CH=CH--C(OCOCH.sub.3)=CH--                  36  do.           do.          *--CH=CH--C(OCOC.sub.2 H.sub.5)=CH--           37  do.           do.          *--CH=CH--C(COOCH.sub.2 CH.sub.2 CH.sub.2                                     CH.sub.3)=CH--                                 38  do.           do.          *--CH=CH--C(COOCH.sub.2 C.sub.6 H.sub.5)=CH                                   --                                             39  do.           do.          *--CH=C(NHCOCH.sub.3)--CH=CH--                 40  do.           do.          *--C(SO.sub.2 NH.sub.2)=CH--CH=CH--            41  do.           do.          *--CH=C(Cl)--C(SO.sub. 2 NH.sub.2)=CH--        42  --C.sub.2 H.sub.5                                                                           --C.sub.2 H.sub.5                                                                          *--CH=C(Br)--C(SO.sub.2 NHCH.sub.3)=CH--       43  do.           do.          *--CH=C(Cl)--C[SO.sub.2 N(CH.sub.3).sub.2                                     ]=CH--                                         44  do.           do.          *--CH=C(OC.sub.2 H.sub.5)--CH=CH--             45  do.           do.          *--C(SO.sub.2 NH.sub.2)=CH--CH=CH--            46  do.           do.          *--C(SO.sub.2 NHCH.sub.3)=CH--CH=CH--          47  do.           do.          *--C[SO.sub.2 N(CH.sub.3).sub.2 ]=CH--CH=CH                                   --                                             48  do.           do.          *--C[SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                        ]=CH--CH=CH--                                  49  do.           do.          *--CH=CH--C(CN)=CH--                           50  do.           do.          *--CH=CH--C(CF.sub.3)=CH--                     51  do.           do.          *--C(CH.sub.3)=CH--CH=C(Br)--                  52  do.           do.          *--C(CN)=CH--CH=CH--                           53  do.           --CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5                                                     *--CH=CH--CH=C(CF.sub.3)--                     54  do.           --C.sub.2 H.sub.5                                                                          *--CH=CH--CH=(OCH.sub.3)--                     55  do.           do.          *--CH=CH= CH=C(CN)--                           56  --C.sub.2 H.sub.5                                                                           --C.sub.2 H.sub.5                                                                          *--N=CH--N=CH--                                57  do.           do.          *--N=C(NHCOCH.sub.3)--N=C(NHCOCH.sub.3)--      58  do.           do.          *--CH=CH--N=CH--                               59  do.           do.          *--C(SO.sub.2 NH.sub.2)=CH--N=CH--             __________________________________________________________________________

The following dyestuffs too can be produced according to the directionsgiven in the first Example, and their properties correspond generally tothe products quoted previously. ##SPC15##

    Example 60         R.sub.10 = H                                               Example 61         R.sub.10 = --SO.sub.2 NH.sub.2                             Example 62         R.sub.10 = --SO.sub.2 NHCH.sub.3                           Example 63         R.sub.10 = --SO.sub.2 N(CH.sub.3).sub.2.               

APPLICATION EXAMPLE

7 Parts of the dyestuff produced according to Example 1 (formula Ie) areground to a fine powder in a ball mill during 48 hours together with 4parts dinaphthyl methane sodium disulphonate, 4 parts sodium cetylsulphate and 5 parts anhydrous sodium sulphate.

1 Part of the dye preparation obtained in this way is mixed to a pastewith a little water, and the resulting suspension is added through asieve to a dye bath consisting of 3 parts sodium lauryl sulphate in 4000parts water. The liquor ratio is 1 : 40. 100 Parts cleaned polyesterfiber material are then put into the bath at 40° - 50° and 20 parts ofan emulsified chlorinated benzole are added. The bath is heated slowlyto 100° and dyeing is applied for 1 - 2 hours at 95° - 100°. The fibresare dyed a brilliant yellow with a greenish tinge. They are washed,soaped, washed again and dried. The level dyeing has good fastness tolight, cross-dyeing, washing, water, sea water, perspiration,sublimation, flue gas, thermosetting, pleating and permanent pressing.

What is claimed is:
 1. A compound of formula Ia, ##SPC16##wherein X isoxygen or NH, R₅ is alkyl which is unsubstituted or substituted byhydroxy, alkoxy, cyano, formyloxy, alkylcarbonyloxy, alkoxycarbonyloxy,alkoxycarbonyl, benzoyloxy, allyl or phenyl; R₆ is hydrogen or one ofthe significances of R₅ ; and ring B is unsubstituted or substituted bychloro, bromo, methyl, alkoxy, cyano, thiocyano, trifluoromethyl,alkoxycarbonyl, benzyloxycarbonyl, alkylcarbonyloxy, acetylamino,propionylamino, benzoylamino, aminosulphonyl, alkylaminosulphonyl,dialkylaminosulphonyl, phenylaminosulphonyl orN-alkyl-N-phenylaminosulphonyl; and the alkyl and alkoxy named contain 1to 4 carbon atoms.
 2. A compound according to claim 1 of formula Ib,##SPC17##wherein X is as defined in claim 17; R₁₁ is ethyl which isunsubstituted or substituted by cyano, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy orethoxycarbonyloxy; R₁₂ is allyl, phenyl or one of the significances ofR₁₁ ; and ring B is unsubstituted or substituted by chloro, bromo,methyl, methoxy, ethoxy, cyano, thiocyano, trifluoromethyl,methoxycarbonyl, ethoxycarbonyl, aminosulphonyl, methylaminosulphonyl ordimethylaminosulphonyl.
 3. A compound according to claim 2 of formulaIc, ##SPC18##wherein R₁₁, r₁₂ and X are as defined in claim 18; R₁₄ andR₁₆ each, independently, are hydrogen, chloro, bromo, methyl, methoxy,cyano or trifluoromethyl; R₁₅ is methoxycarbonyl, ethoxycarbonyl or oneof the significances of R₁₄ and R₁₆ ; and R₁₇ is aminosulphonyl,methylaminosulphonyl, dimethylaminosulphonyl or one of the significancesor R₁₄ and R₁₆.
 4. A compound according to claim 1 of the formula##SPC19##wherein ring B is unsubstituted or substituted by one or twosubstituents selected from methyl, chloro, trifluoromethyl and methoxy.5. A compound according to claim 1 of the formula ##SPC20##
 6. Acompound according to claim 1 of the formula ##SPC21##
 7. A compoundaccording to claim 1 of the formula ##SPC22##
 8. A compound according toclaim 1 of the formula ##SPC23##
 9. A compound according to claim 1 ofthe formula ##SPC24##
 10. A compound according to claim 17 of theformula ##SPC25##